US20040039115A1 - Polyethylene resin composition - Google Patents
Polyethylene resin composition Download PDFInfo
- Publication number
- US20040039115A1 US20040039115A1 US10/415,365 US41536503A US2004039115A1 US 20040039115 A1 US20040039115 A1 US 20040039115A1 US 41536503 A US41536503 A US 41536503A US 2004039115 A1 US2004039115 A1 US 2004039115A1
- Authority
- US
- United States
- Prior art keywords
- resin composition
- component
- polyethylene
- molecular weight
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 178
- 229920013716 polyethylene resin Polymers 0.000 title claims abstract description 104
- 238000005299 abrasion Methods 0.000 claims abstract description 55
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims abstract description 53
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims abstract description 53
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 46
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims abstract description 28
- 239000004698 Polyethylene Substances 0.000 claims description 35
- -1 polyethylene Polymers 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 229920000573 polyethylene Polymers 0.000 claims description 20
- 239000004576 sand Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 229920001038 ethylene copolymer Polymers 0.000 claims description 9
- 239000004711 α-olefin Substances 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 238000000465 moulding Methods 0.000 description 17
- 238000002156 mixing Methods 0.000 description 12
- 239000003381 stabilizer Substances 0.000 description 11
- 229920000098 polyolefin Polymers 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 9
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 230000001627 detrimental effect Effects 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 150000004291 polyenes Chemical class 0.000 description 3
- 239000012748 slip agent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000005671 trienes Chemical class 0.000 description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 2
- FDBMBOYIVUGUSL-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FDBMBOYIVUGUSL-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000008262 pumice Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- WUMAAEAEKPYOSF-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-butyl-6-tert-butylphenol Chemical compound CC(C)(C)C1=CC(CCCC)=CC(N2N=C3C=CC=CC3=N2)=C1O WUMAAEAEKPYOSF-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- QROGOPRRETUDKB-UHFFFAOYSA-N 4-butyl-2-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol Chemical compound CC(C)(C)C1=CC(CCCC)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O QROGOPRRETUDKB-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- HSWXIPBJUXFYPH-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(C(=O)OP(OC(C2=CC(=C(C(=C2)C(C)(C)C)O)C(C)(C)C)=O)(O)=O)C=C(C=1O)C(C)(C)C Chemical compound C(C)(C)(C)C=1C=C(C(=O)OP(OC(C2=CC(=C(C(=C2)C(C)(C)C)O)C(C)(C)C)=O)(O)=O)C=C(C=1O)C(C)(C)C HSWXIPBJUXFYPH-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QAEPIAHUOVJOOM-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC QAEPIAHUOVJOOM-UHFFFAOYSA-N 0.000 description 1
- PWZDGWCRBINXHV-UHFFFAOYSA-N OP(O)OP(O)O.OCC(CO)(CO)CO.C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO.C=1C=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PWZDGWCRBINXHV-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
Definitions
- the present invention relates to a polyethylene resin composition having an excellent balance of properties, such as abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance and moldability. More particularly, the invention relates to a polyethylene resin composition having an excellent balance between abrasion resistance, appearance and moldability.
- Ultra-high-molecular weight polyethylene has lower intermolecular cohesive force, more symmetric molecular structure and higher crystallinity ,thereby has excellent sliding properties, as compared with general-purpose resins such as ordinary polyethylene, and besides it is excellent in impact strength, abrasion resistance, tensile strength, etc., so that it can be used as, for example, a sliding material.
- the ultra-high-molecular weight polyethylene is simply blended with polyethylene having a low intrinsic viscosity [ ⁇ ]
- the abrasion resistance is not improved conspicuously because the ultra-high-molecular weight polyethylene has bad compatibility with the polyethylene having a low intrinsic viscosity [ ⁇ ]
- the blend exhibits poor impact strength and appearance (e.g., Japanese Patent Laid-Open Publication No. 240748/1985, Japanese Patent Laid-Open Publication No. 129047/1989, Japanese Patent Laid-Open Publication No. 156344/1989).
- a polyolefin composition for injection molding which. comprises 15 to 40% by weight of ultra-high-molecular weight polyolefin having an intrinsic viscosity [ ⁇ ] of 10 to 40 dl/g and 85 to 60% by weight of low-molecular weight to high-molecular weight polyolefin having an intrinsic viscosity [ ⁇ ] of 0.1 to 5 dl/g, is disclosed.
- This composition is epoch-making for the reasons that the composition can be subjected to injection molding in spite that it contains the ultra-high-molecular weight polyolefin and a molded article obtainable from the composition by injection molding has excellent sliding properties and abrasion resistance inherent in the ultra-high-molecular weight polyolefin.
- the above composition however, has limitations in the flexibility and the abrasion resistance when it is used alone, because the amount of the ultra-high-molecular weight polyolefin is in the range of 15 to 40% by weight.
- a molded product having remarkably enhanced and well-balanced properties such as abrasion resistance, self-lubricating properties, appearance, hardness (from flexible to rigid) and molding properties
- a polyethylene resin composition (A) which is obtained by multi-step polymerization and comprises ultra-high-molecular weight polyethylene (component (a-1)) and low-molecular weight to high-molecular weight polyethylene (component (a-2)) in a specific ratio and then molding the resin composition, or by melt blending the resin composition (A) with a polyolefin resin composition (B) having specific properties, such as a flexible composition, a rigid composition, a composition of a wide molecular weight distribution appropriate to covering or a polyethylene resin composition of high flowability appropriate to injection molding, and then molding the resin composition. Based on the finding, the present invention has been accomplished.
- the polyethylene resin composition according to the present invention is a polyethylene resin composition (A) which comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [ ⁇ ] of 10 to 40 dl/g in an amount of more than 35% by weight and not more than 90% by weight and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [ ⁇ ] of 0.1 to 5 dl/g in an amount of not less than 10% by weight and less than 65% by weight, and which has a density of 930 to 980 kg/m 3 and an intrinsic viscosity [ ⁇ ] of 5 to 35 dl/g.
- This polyethylene resin composition (A) is employable as a resin modifier.
- the polyethylene resin composition according to the present invention also is a polyethylene resin composition (C) comprising a resin modifier that is the polyethylene resin composition (A) and a polyolefin resin composition (B) containing at least an ethylene (co)polymer having an intrinsic viscosity [ ⁇ ] of 0.1 to 10 dl/g.
- the present invention is specified by the following items (1) to (9).
- a resin modifier comprising a polyethylene resin composition (A) which comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [ ⁇ ] of 10 to 40 dl/g and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [ ⁇ ] of 0.1 to 5 dl/g, wherein:
- the amount of the component (a-1) is more than 35% by weight and not more than 90% by weight and the amount of the component (a-2) is not less than 10% by weight and less than 65% by weight, based on the total amount of the component (a-1) and the component (a-2), and
- the polyethylene resin composition (A) has a density of 930 to 980 kg/m 3 and an intrinsic viscosity [ ⁇ ] of 5 to 35 dl/g.
- a polyethylene resin composition (C) comprising 15 to 90% by weight of a polyethylene resin composition (A) and 85 to 10% by weight of a polyolefin resin composition (B), wherein:
- the polyethylene resin composition (A) comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [ ⁇ ] of 10 to 40 dl/g and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [ ⁇ ] of 0.1 to 5 dl/g,
- the amount of the component (a-1) is more than 35% by weight and not more than 90% by weight and the amount of the component (a-2) is not less than 10% by weight and less than 65% by weight, based on the total amount of the component (a-1) and the component (a-2),
- the polyethylene resin composition (A) has a density of 930 to 980 kg/m 3 and an intrinsic viscosity [ ⁇ ] of 5 to 35 dl/g, and
- the polyolefin resin composition (B) contains at least an ethylene (co)polymer having an intrinsic viscosity [ ⁇ ] of 0.1 to 10 dl/g.
- a process for preparing a polyethylene resin composition which comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [ ⁇ ] of 10 to 40 dl/g and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [ ⁇ ] of 0.1 to 5 dl/g, the amount of said component (a-1) being more than 35% by weight and not more than 90% by weight, the amount of said component (a-2) being not less than 10% by weight and less than 65% by weight, each amount being based on the total amount of the component (a-1) and the component (a-2), and which has a density of 930 to 980 kg/m 3 and an intrinsic viscosity [ ⁇ ] of 5 to 35 dl/g,
- a covering material or a sliding material comprising a resin composition containing at least 2 to 40% by weight of ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [ ⁇ ] of 10 to 40 dl/g, and
- the resin composition according to the present invention is described in detail hereinafter.
- the resin composition of the present invention is a polyethylene resin composition (A) comprising a component (a-1) and a component (a-2) or a polyethylene resin composition (C) comprising the polyethylene resin composition (A) and further a polyolefin resin composition (B).
- the polyethylene resin composition (A) for use in the invention which comprises the component (a-1) and the component (a-2), is described.
- the polyethylene resin composition (A) for use in the present invention comprises ultra-high-molecular weight polyethylene and low-molecular weight to high-molecular weight polyethylene, and is mainly used as a resin modifier.
- the ultra-high-molecular weight polyethylene and the low-molecular weight to high-molecular weight polyethylene for constituting the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) are each a homopolymer of ethylene or a copolymer of ethylene and an ⁇ -olefin, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene or 3-methyl-1-pentene.
- ultra-high-molecular weight polyethylene or the low-molecular weight to high-molecular weight polyethylene is a homopolymer of ethylene or a copolymer of ethylene and the above ⁇ -olefin which contains ethylene as a main ingredient.
- the ultra-high-molecular weight polyethylene (component (a-1)) for constituting the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) is polyethylene having an intrinsic viscosity [ ⁇ ], as measured in a decalin solvent at 135° C., of 10 to 40 dl/g, preferably 15 to 35 dl/g, more preferably 20 to 35 dl/g, and can be obtained by polymerization of the first step.
- the low-molecular weight to high-molecular weight polyethylene (component (a-2)) is polyethylene having an intrinsic viscosity [ ⁇ ], as measured in a decalin solvent at 135° C. similarly to the above, of 0.1 to 5 dl/g, preferably 0.5 to 3 dl/g, more preferably 1.0 to 2.5 dl/g, and can be obtained by polymerization of the second step after the formation of the ultra-high-molecular weight polyethylene.
- the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) can be prepared by polymerizing ethylene in multiple steps in the presence of a catalyst, and the multi-step polymerization can be carried out in the same manner as the polymerization described in Japanese Patent Laid-Open Publication No. 289636/1990.
- the ultra-high-molecular weight polyethylene component (a-1)
- the low-molecular weight to high-molecular weight polyethylene component (a-2)
- having an intrinsic viscosity [ ⁇ ] of the above range is formed by the post-polymerization, whereby the compatibility with the later-described polyolefin resin composition (B) is enhanced, and as a result, the ultra-high-molecular weight polyethylene is homogeneously dispersed and combined.
- a polyethylene resin composition having an excellent balance of properties, such as abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance and moldability, particularly an excellent balance between abrasion resistance, appearance and moldability, can be obtained.
- the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) contains the ultra-high-molecular weight polyethylene (component (a-1)) and the low-molecular weight to high-molecular weight polyethylene (component (a-2)) in a specific ratio.
- the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) contains the ultra-high-molecular weight polyethylene (component (a-1)) in an amount of more than 35% by weight and not more than 90% by weight, preferably more than 40% by weight and not more than 80% by weight, more preferably 45 to 80% by weight, and contains the low-molecular weight to high-molecular weight polyethylene (component (a-2)) in an amount of not less than 10% by weight and less than 65% by weight, preferably not less than 20% by weight and less than 60% by weight, more preferably 20 to 55% by weight.
- a resin composition containing ultra-high-molecular weight polyethylene of large particles can be obtained, and besides a resin composition can be improved in the compatibility with the polyolefin resin composition (B) and particularly excellent abrasion resistance, appearance and moldability can be obtained.
- the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) substantially consists of the ultra-high-molecular weight polyethylene (component (a-1)) and the low-molecular weight to high-molecular weight polyethylene (component (a-2)).
- the sum of the content of the ultra-high-molecular weight polyethylene (component (a-1)) and the content of the low-molecular weight to high-molecular weight polyethylene (component (a-2)) in the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) is usually 100% by weight.
- the polyethylene resin composition (A) may contain, in addition to the above components, additives which may be added to ordinary polyolefins (such as stabilizer, e.g., heat stabilizer, weathering stabilizer, crosslinking agent, crosslinking assistant, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, filler, mineral oil type softener, petroleum resin and wax) within limits not detrimental to the objects of the present invention.
- additives which may be added to ordinary polyolefins (such as stabilizer, e.g., heat stabilizer, weathering stabilizer, crosslinking agent, crosslinking assistant, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, filler, mineral oil type softener, petroleum resin and wax) within limits not detrimental to the objects of the present invention.
- additives which may be added to ordinary polyolefins (such as stabilizer, e.g., heat stabilize
- the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2), which substantially consists of the ultra-high-molecular weight polyethylene and the low-molecular weight to high-molecular weight polyethylene, has a density, as measured in accordance with ASTM D1505, of 930 to 980 kg/m 3 , preferably 940 to 980 kg/m 3 .
- the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2.) has an intrinsic viscosity [ ⁇ ], as measured in a decalin solvent at 135° C., of 5 to 35 dl/g, preferably 10 to 30 dl/g, more preferably 12 to 28 dl/g.
- the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) has a density of the above range, a molded product of the composition has a low coefficient of dynamic friction and thereby exhibits excellent self-lubricating properties.
- the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) has an intrinsic viscosity [ ⁇ ] of the above range
- the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B) can be well dispersed in each other.
- the low-molecular weight to high-molecular weight polyethylene contained in the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B) are finely dispersed in each other to give a homogeneously dispersed state when they are melt blended by an extruder or the like. Therefore, by the use of the resin composition, a molded product having excellent abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance and moldability can be obtained.
- the polyethylene resin composition (A) can improve abrasion resistance, self-lubricating properties and the like when it is blended with other resins, so that it can be favorably used as a resin modifier.
- the resin to be modified is not specifically restricted, preferable is a polyolefin resin composition (B).
- the polyolefin resin composition (B) for use in the present invention is not specifically restricted as far as it is a resin composition containing at least an ethylene (co)polymer having an intrinsic viscosity [ ⁇ ] of 0.1 to 10 dl/g.
- ethylene (co)polymers examples include high-pressure polyethylene, medium- or low-pressure polyethylene, an ethylene/ ⁇ -olefin copolymer, an ethylene/vinyl alcohol copolymer, an ethylene/vinyl acetate copolymer, an ethylene/vinyl acetate copolymer saponified product, an ethylene/(meth)acrylic acid copolymer and an ethylene/ ⁇ -olefin/diene (triene, polyene) terpolymer.
- Examples of the ⁇ -olefins include olefins of 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene and 3-methyl-1-pentene.
- Examples of the dienes (trienes, polyenes) include conjugated or non-conjugated dienes, trienes and polyenes, such as 5-ethylidene-2-norbornene and vinyl norbornene.
- the above ethylene (co)polymers may be used singly, or a resin composition composed of two or more of the ethylene (co)polymers may be used, or a resin composition composed of the ethylene (co)polymer and another polyolefin such as polypropylene or polybutene may be used.
- the polyolefin resin composition (B) is polyethylene
- the polyethylene has a density of 820 to 980 kg/m 3 , preferably 850 to 970 kg/m 3 , more preferably 860 to 960 kg/m 3 , and has an intrinsic viscosity [ ⁇ ] of 0.1 to 10 dl/g, preferably 0.2 to 8 dl/g, more preferably 0.3 to 6 dl/g.
- the resin preferably contained in the polyolefin resin composition (B) not only the above-mentioned polyethylene having a density of 820 to 980 kg/m 3 and an intrinsic viscosity [ ⁇ ] of 0.1 to 10 dl/g but also a resin composition composed of polypropylene and an ethylene/ ⁇ -olefin/diene copolymer, or an ethylene/vinyl alcohol copolymer can be mentioned.
- the polyolefin resin composition (B) for use in the present invention is a resin composition containing at least the ethylene (co)polymer having an intrinsic viscosity [ ⁇ ] of 0.1 to 10 dl/g
- the polyolefin resin composition (B) and the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) can be well dispersed in each other.
- the polyolefin resin composition (B) and the low-molecular weight to high-molecular weight polyethylene contained in the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) are finely dispersed in each other to give a homogeneously dispersed state when they are melt blended by an extruder or the like. Therefore, by the use of the resin composition, a molded product having excellent abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance and moldability can be obtained.
- the polyolefin resin composition (B) in the present invention may contain additives which may be added to ordinary polyolefins (such as stabilizer, e.g., heat stabilizer, weathering stabilizer, crosslinking agent, crosslinking assistant, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, filler, mineral oil type softener, petroleum resin and wax) within limits not detrimental to the objects of the present invention.
- additives which may be added to ordinary polyolefins (such as stabilizer, e.g., heat stabilizer, weathering stabilizer, crosslinking agent, crosslinking assistant, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, filler, mineral oil type softener, petroleum resin and wax) within limits not detrimental to the objects of the present invention.
- the polyethylene resin composition (C) according to the present invention comprises the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B).
- the compounding ratio between the polyethylene resin composition (A) and the polyolefin resin composition (B) is as follows: the proportion of the polyethylene resin composition (A) is in the range of 15 to 90% by weight and the proportion of the polyolefin resin composition (B) is in the range of 85 to 10% by weight; preferably, the proportion of the polyethylene resin composition (A) is in the range of 20 to 80% by weight and the proportion of the polyolefin resin composition (B) is in the range of 80 to 20% by weight; more preferably, the proportion of the polyethylene resin composition (A) is in the range of 40 to 60% by weight and the proportion of the polyolefin resin composition (B) is in the range of 60 to 40% by weight.
- the amount of the ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [ ⁇ ] of 10 to 40 dl/g contained in the polyethylene resin composition (C) is in the range of 2 to 40% by weight, preferably 5 to 30% by weight, more preferably 10 to 25% by weight.
- the polyethylene resin composition (C) of the present invention has the above-mentioned compounding ratios
- the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B) can be well dispersed in each other.
- the polyolefin resin composition (B) and the low-molecular weight to high-molecular weight polyethylene contained in the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) are finely dispersed in each other to give a homogeneously dispersed state when they are melt blended by an extruder or the like.
- the polyethylene resin composition (C) of the present invention has a melt flow rate (MFR, 190° C., load of 10 kg) of not less than 6, preferably not less than 7, more preferably not less than 8.
- MFR melt flow rate
- the sand abrasion wear of a sheet of 3 mm thickness obtained from the polyethylene resin composition (C), as measured in a sand abrasion test, is not more than 59 mg, preferably not more than 55 mg, more preferably not more than 52 mg.
- the limiting PV value of a sheet of 3 mm thickness obtained from the polyethylene resin composition (C) is not less than 0.30 (MPa ⁇ m/s), preferably not less than 0.35, more preferably not less than 0.40.
- the sum of the content of the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the content of the polyolefin resin composition (B) in the polyethylene resin composition (C) of the invention is 100% by weight.
- the composition (C) of the invention may be added other resins within limits not detrimental to the objects of the present invention.
- the polyethylene resin composition (C) of the present invention contains, as its essential components, the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B), but to the composition (C) may be further added additives, such as filler, stabilizer, e.g., heat stabilizer, weathering stabilizer, crosslinking agent, crosslinking assistant, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, mineral oil type softener, petroleum resin and wax, within limits not detrimental to the objects of the present invention.
- additives such as filler, stabilizer, e.g., heat stabilizer, weathering stabilizer, crosslinking agent, crosslinking assistant, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, mineral oil type softener, petroleum resin and wax, within limits not detrimental to the objects of the present invention.
- ultraviolet absorbing agents examples include benzophenone compounds, benzotriazole compounds, nickel compounds and hindered amine compounds. Specific examples of such compounds include 2,2′,4,4′-tetrahydroxybenzophenone, 2-(2′-hydroxy-3′-t-butyl-5′-butylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′-t-butyl-5′-butylphenyl)benzotriazole, nickel salt of bis(3,5-di-t-butyl-4-hydroxybenzoyl)phosphoric acid ethyl ester and bis(2,2′,6,6′-tetramethyl-4-piperidine)sebacate.
- benzophenone compounds examples include 2,2′,4,4′-tetrahydroxybenzophenone, 2-(2′-hydroxy-3′-t-butyl-5′-butylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′-t-butyl-5′
- Examples of the stabilizers arbitrarily added include phenolic antioxidants, such as tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, ⁇ -(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester and 2,2′-oxamidobis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; and fatty acid metallic salts, such as zinc stearate, calcium stearate and calcium 1,2-hydroxystearate.
- phenolic antioxidants such as tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, ⁇ -(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester and 2,2′-oxamidobis[ethyl-3
- the above compounds may be used in combination.
- tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane and zinc stearate or calcium stearate may be used in combination.
- phosphorus type stabilizers such as distearyl pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl-4,4′-isopropylidenediphenol-pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, phenylbisphenol A-pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetrakis(2,4-di-t-butylpheny
- the above stabilizers can be used singly or in combination of two or more kinds.
- the polyethylene resin composition (C) of the present invention may contain organic fillers or inorganic fillers when needed, within limits not detrimental to the objects of the present invention.
- silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, glass flake, glass bead, Shirasu bead, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder and molybdenum sulfide may be contained.
- a known process comprising preparing the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B) separately and melt kneading the polyethylene resin composition (A) and the polyolefin resin composition (B) by an extruder is available.
- melt kneading is carried out at a temperature of 180 to 400° C.
- an extruder used for ordinary polyolefin resins is employable, but from the viewpoint of kneading effect, a twin-screw extruder or a tandem extruder is preferable.
- a molded product of desired shape can be obtained by molding the polyethylene resin composition (C) by a known molding method.
- the polyethylene resin composition can be molded into products of various shapes, such as container, tray, sheet, bar and film, or into coverings of various molded products.
- the molded products obtained as above can be widely applied to the conventionally known polyethylene uses. Because of their particularly excellent balance of properties, such as abrasion resistance, self-lubricating properties, impact strength and thin wall molding properties, the molded products can be applied to uses where such properties are required, for example, covering (lamination) of metallic products, such as steel pipe, electric wire and automobile slide door rail; covering (lamination) of various rubber products, such as pressure-resistant rubber hose, automobile door gasket, clean room door gasket, automobile glass run channel and automobile weather strip; lining of hopper and chute; and sliding materials, such as gear, bearing, roller, tape reel, various guide rails, elevator rail guide and various protective liners.
- metallic products such as steel pipe, electric wire and automobile slide door rail
- covering (lamination) of various rubber products such as pressure-resistant rubber hose, automobile door gasket, clean room door gasket, automobile glass run channel and automobile weather strip
- lining of hopper and chute and sliding materials, such as gear, bearing, roller, tape reel, various guide rails, elevator rail
- the thickness of the covering material is in the range of 10 to 200 ⁇ m, preferably 20 to 100 ⁇ m.
- the polyethylene resin composition (C) as the covering (lamination) material, further, it is preferable that any sea-island structure is not observed on the surface of the resin composition by an electron microscope of 500 ⁇ magnification, or even if it is observed, the island has an average particle diameter of not more than 20 ⁇ m.
- the flexural modulus of the polyethylene resin composition (C) is desired to be not more than 1500 MPa, preferably not more than 1300 MPa, more preferably not more than 1000 MPa.
- the tensile elongation at break of the polyethylene resin composition (C) is desired to be not less than 10%, preferably not less than 20%, more preferably not less than 30%.
- Ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [ ⁇ ] of 30 dl/g and low-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [ ⁇ ] of 1.5 dl/g were produced in the weight ratio shown in Table 1 through two-step polymerization and then diluted by blending with, as the polyolefin resin composition (B), high-density low-molecular weight polyethylene (available from Mitsui Chemicals, Inc., trade name: Hizex 1700JP) having an intrinsic viscosity [ ⁇ ] of 1.1 dl/g and a density of 965 kg/m 3 in the weight ratio shown in Table 1 so that the concentration of the ultra-high-molecular weight polyethylene (component (a-1)) in the resulting resin composition became 20% by weight. After the blending, the resin composition was melt blended by a PCM twin-screw extruder manufactured by Ikegai Ltd. to prepare pellet
- Ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [ ⁇ ] of 30 dl/g and low-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [ ⁇ ] of 1.5 dl/g were produced in the weight ratio shown in Table 2 through two-step polymerization and then diluted by blending with, as the polyolefin resin composition (B), high-molecular weight polyethylene (available from Mitsui Chemicals, Inc., trade name: Hizex 5100E) having an intrinsic viscosity [ ⁇ ] of 2.6 dl/g and a density of 944 kg/m 3 in the weight ratio shown in Table 2 so that the concentration of the ultra-high-molecular weight polyethylene (component (a-1)) in the resulting resin composition became 20% by weight. After the blending, the resin composition was melt blended by a PCM twin-screw extruder manufactured by Ikegai Ltd. to prepare pellets.
- the resultant blend was subjected to injection molding to prepare a test piece (sheet having a thickness of 3 mm), and the test piece was subjected to a sand abrasion test and a limiting PV value measuring test in accordance with the test methods described later. Further, measurements of a flexural modulus and a tensile elongation at break of the test piece were carried out.
- Linear polyethylene produced by two-step polymerization and containing ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [ ⁇ ] of 30 dl/g and low-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [ ⁇ ] of 1.5 dl/g in the weight ratio shown in Table 1 was diluted by blending with, as the polyolefin resin composition (B), high-density low-molecular weight polyethylene (available from Mitsui Chemicals, Inc., trade name: Hizex 1700JP) having an intrinsic viscosity [ ⁇ ] of 1.1 dl/g and a density of 965 kg/m 3 in the weight ratio shown in Table 3.
- the resin composition was melt blended by a PCM twin-screw extruder manufactured by Ikegai Ltd. to prepare pellets.
- a stirring vessel a mixture liquid of 3 kg of water and 2.6 kg of abrasive grains (JIS R6001 (A-43)) was placed, and 4 plates (test pieces) having a width of 25 mm, a length of 75 mm and a thickness of 3 mm were set on the stirring blade in such a manner that the angle between the plate and the mixture liquid was 45° . Then, the stirring blade was rotated at a rate of 1600 rpm for 3 hours to measure a sand abrasion wear. In a jacket of the stirring vessel, cooling water of 25° C. was circulated.
- the abrasion resistance was evaluated as follows. From the weight of the test piece before the test, the weight of the test piece after the test was subtracted to obtain an abrasion wear (mg) of the sample. A test piece having a sand abrasion wear of not more than 59 mg was evaluated as AA (pass). (Sand abrasion wear of conventional one (Comparative Example 1): not less than 60 mg) (See Table 1, Table 2 and Table 3)
- the self-lubricating properties were evaluated as follows.
- a metal plate SUS-304
- the test piece was abraded by a friction-abrasion tester (manufactured by KK Orientech, EFM-H1-ENS) with maintaining the peripheral velocity (V) constant at 0.2 m/s and increasing a load (P) every 30 minutes by 5 kg ⁇ f, and a load at which the test piece began to melt by frictional heat was measured to find a limiting PV value (MPa ⁇ m/s).
- a test piece having a limiting PV value of not less than 0.3 was evaluated as AA (pass).
- (Limiting PV value of ultra-high-molecular weight polyethylene conventionally used: not less than 0.28) See Table 1, Table 2 and Table 3
- the polyethylene resin composition according to the present invention comprises a polyethylene resin composition (A) comprising an ultra-high-molecular weight polyethylene component and a low-molecular weight to high-molecular weight polyethylene component or comprises the polyethylene resin composition (A) and a specific polyolefin resin composition (B), it has not only excellent abrasion resistance and mechanical properties inherent in the ultra-high-molecular weight polyethylene but also specific properties of the low-molecular weight to high-molecular weight polyethylene and/or the polyolefin resin composition (B). Hence, a molded product having an excellent balance of properties, such as abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance, flexibility and molding properties, particularly an excellent balance between abrasion resistance, appearance and molding properties, can be obtained.
- the polyethylene resin composition of the present invention can be favorably used as a material of an injection molded product, a covering (lamination) material for various molded products such as steel pipe, pressure-resistant rubber hose, electric wire and sheet, or a sliding material.
- An effect of the present invention is that a polyethylene resin composition exhibiting at least the following properties (1) to (4) at the same time can be provided.
- Another effect of the present invention is that a polyethylene resin composition, in a preferred embodiment, exhibiting the following properties (1) to (8) at the same time can be provided:
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A polyethylene resin composition comprising 15 to 90% by weight of a polyethylene resin composition (A) and 85 to 10% by weight of a polyolefin resin composition (B), wherein the polyethylene resin composition (A) comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 0.1 to 5 dl/g, the amount of said component (a-1) being more than 35% by weight and not more than 90% by weight, the amount of said component (a-2) being not less than 10% by weight and less than 65% by weight, each amount being based on the total amount of the component (a-1) and the component (a-2), and the polyethylene resin composition (A) has a density of 930 to 980 kg/m3 and an intrinsic viscosity [η] of 5 to 35 dl/g. The polyethylene resin composition is excellent in at least the following properties (1) to (8): (1) mechanical properties (mechanical properties equal to or higher than those of conventional ultra-high-molecular weight polyethylene), (2) abrasion resistance (abrasion resistance remarkably improved or enhanced as compared with that of conventional ultra-high-molecular weight polyethylene), (3) appearance, (4) moldability, (5) self-lubricating properties, (6) chemical resistance, (7) impact resistance (impact strength), and (8) flexibility.
Description
- The present invention relates to a polyethylene resin composition having an excellent balance of properties, such as abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance and moldability. More particularly, the invention relates to a polyethylene resin composition having an excellent balance between abrasion resistance, appearance and moldability.
- Ultra-high-molecular weight polyethylene has lower intermolecular cohesive force, more symmetric molecular structure and higher crystallinity ,thereby has excellent sliding properties, as compared with general-purpose resins such as ordinary polyethylene, and besides it is excellent in impact strength, abrasion resistance, tensile strength, etc., so that it can be used as, for example, a sliding material.
- From the ultra-high-molecular weight polyethylene, however, a molded product is hardly produced because of its high molecular weight, and in many cases, it is difficult to apply the technique commonly used for molding the general-purpose polyethylene to the ultra-high-molecular weight polyethylene.
- Further, even if the ultra-high-molecular weight polyethylene is simply blended with polyethylene having a low intrinsic viscosity [η], the abrasion resistance is not improved conspicuously because the ultra-high-molecular weight polyethylene has bad compatibility with the polyethylene having a low intrinsic viscosity [η], and besides, the blend exhibits poor impact strength and appearance (e.g., Japanese Patent Laid-Open Publication No. 240748/1985, Japanese Patent Laid-Open Publication No. 129047/1989, Japanese Patent Laid-Open Publication No. 156344/1989).
- Therefore, various proposals have been made in order to impart excellent moldability to the ultra-high-molecular weight polyethylene without impairing the excellent properties of the ultra-high-molecular weight polyethylene.
- For example, in Japanese Patent Laid-Open Publication No. 12606/1988, a polyolefin composition for injection molding, which. comprises 15 to 40% by weight of ultra-high-molecular weight polyolefin having an intrinsic viscosity [η] of 10 to 40 dl/g and 85 to 60% by weight of low-molecular weight to high-molecular weight polyolefin having an intrinsic viscosity [η] of 0.1 to 5 dl/g, is disclosed.
- This composition is epoch-making for the reasons that the composition can be subjected to injection molding in spite that it contains the ultra-high-molecular weight polyolefin and a molded article obtainable from the composition by injection molding has excellent sliding properties and abrasion resistance inherent in the ultra-high-molecular weight polyolefin.
- The above composition, however, has limitations in the flexibility and the abrasion resistance when it is used alone, because the amount of the ultra-high-molecular weight polyolefin is in the range of 15 to 40% by weight.
- If the amount of the ultra-high-molecular weight polyolefin is increased within the above range, the abrasion resistance is improved to some extent, but the injection molding becomes difficult, the appearance is bad, and there is room for improvement in the abrasion resistance, moldability and appearance.
- It is an object of the present invention to provide a polyethylene resin composition exhibiting at least the following properties (1) to (4) at the same time.
- It is another object of the present invention to provide a polyethylene resin composition, in a preferred embodiment, exhibiting the following properties (1) to (8) at the same time:
- (1) excellent mechanical properties (mechanical properties equal to or higher than those of conventional ultra-high-molecular weight polyethylene),
- (2) excellent abrasion resistance (abrasion resistance remarkably improved or enhanced as compared with that of conventional ultra-high-molecular weight polyethylene),
- (3) excellent appearance,
- (4) excellent moldability,
- (5) excellent self-lubricating properties,
- (6) excellent chemical resistance,
- (7) excellent impact resistance (impact strength), and
- (8) moderate flexibility.
- In view of such problems associated with the prior art as described above, the present inventor has earnestly studied resin compositions having an excellent balance of properties, such as abrasion resistance, self-lubricating properties, appearance and moldability, which are favorably used as covering materials for tubes, hoses and metallic pipes or materials of sliding parts which are injection molded articles. As a result, the present inventor has found that a molded product having remarkably enhanced and well-balanced properties, such as abrasion resistance, self-lubricating properties, appearance, hardness (from flexible to rigid) and molding properties, can be obtained by melt blending a polyethylene resin composition (A) which is obtained by multi-step polymerization and comprises ultra-high-molecular weight polyethylene (component (a-1)) and low-molecular weight to high-molecular weight polyethylene (component (a-2)) in a specific ratio and then molding the resin composition, or by melt blending the resin composition (A) with a polyolefin resin composition (B) having specific properties, such as a flexible composition, a rigid composition, a composition of a wide molecular weight distribution appropriate to covering or a polyethylene resin composition of high flowability appropriate to injection molding, and then molding the resin composition. Based on the finding, the present invention has been accomplished.
- That is to say, the polyethylene resin composition according to the present invention is a polyethylene resin composition (A) which comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g in an amount of more than 35% by weight and not more than 90% by weight and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 0.1 to 5 dl/g in an amount of not less than 10% by weight and less than 65% by weight, and which has a density of 930 to 980 kg/m3 and an intrinsic viscosity [η] of 5 to 35 dl/g. This polyethylene resin composition (A) is employable as a resin modifier.
- The polyethylene resin composition according to the present invention also is a polyethylene resin composition (C) comprising a resin modifier that is the polyethylene resin composition (A) and a polyolefin resin composition (B) containing at least an ethylene (co)polymer having an intrinsic viscosity [η] of 0.1 to 10 dl/g.
- The present invention is specified by the following items (1) to (9).
- (1) A resin modifier comprising a polyethylene resin composition (A) which comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 0.1 to 5 dl/g, wherein:
- the amount of the component (a-1) is more than 35% by weight and not more than 90% by weight and the amount of the component (a-2) is not less than 10% by weight and less than 65% by weight, based on the total amount of the component (a-1) and the component (a-2), and
- the polyethylene resin composition (A) has a density of 930 to 980 kg/m3 and an intrinsic viscosity [η] of 5 to 35 dl/g.
- (2) A polyethylene resin composition (C) comprising 15 to 90% by weight of a polyethylene resin composition (A) and 85 to 10% by weight of a polyolefin resin composition (B), wherein:
- the polyethylene resin composition (A) comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 0.1 to 5 dl/g,
- the amount of the component (a-1) is more than 35% by weight and not more than 90% by weight and the amount of the component (a-2) is not less than 10% by weight and less than 65% by weight, based on the total amount of the component (a-1) and the component (a-2),
- the polyethylene resin composition (A) has a density of 930 to 980 kg/m3 and an intrinsic viscosity [η] of 5 to 35 dl/g, and
- the polyolefin resin composition (B) contains at least an ethylene (co)polymer having an intrinsic viscosity [η] of 0.1 to 10 dl/g.
- (3) The polyethylene resin composition (C) as described in the item (2), wherein the polyolefin resin composition (B) is polyethylene having a density of 820 to 980 kg/m3 and an intrinsic viscosity [η] of 0.1 to 10 dl/g.
- (4) The polyethylene resin composition (C) as described in the item (2), wherein the polyolefin resin composition (B) is a resin composition containing polypropylene and an ethylene/α-olefin/diene copolymer.
- (5) The polyethylene resin composition (C) as described in the item (2), wherein the polyolefin resin composition (B) contains an ethylene/vinyl alcohol copolymer.
- (6) A process for preparing a polyethylene resin composition which comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 0.1 to 5 dl/g, the amount of said component (a-1) being more than 35% by weight and not more than 90% by weight, the amount of said component (a-2) being not less than 10% by weight and less than 65% by weight, each amount being based on the total amount of the component (a-1) and the component (a-2), and which has a density of 930 to 980 kg/m3 and an intrinsic viscosity [η] of 5 to 35 dl/g,
- comprising multi-step polymerization consisting of at least two steps of:
- a first step of polymerizing ethylene in the presence of a Ziegler catalyst to form ultra-high-molecular weight polyethylene having an intrinsic viscosity [η] of 10 to 40 dl/g, and
- a second step of polymerizing ethylene in the presence of the ultra-high-molecular weight polyethylene formed in the first step, a Ziegler catalyst and hydrogen to form low-molecular weight to high-molecular weight polyethylene having an intrinsic viscosity [η] of 0.1 to 5 dl/g.
- (7) The process for preparing a polyethylene resin composition as described in the item (6), wherein the Ziegler catalyst comprises a high-activity titanium catalyst component containing magnesium, titanium and halogen as essential ingredients and an organoaluminum compound catalyst component.
- (8) A covering material or a sliding material made of a resin having a melt flow rate (190° C., load of 10 kg) of not less than 6, a sand abrasion wear, as measured on a sheet having a thickness of 3 mm in a sand abrasion test, of not more than 59 mg, and a limiting PV value, as measured on a sheet having a thickness of 3 mm, of not less than 0.30 (MPa·m/s).
- (9) A covering material or a sliding material comprising a resin composition containing at least 2 to 40% by weight of ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g, and
- having a sand abrasion wear, as measured on a sheet having a thickness of 3 mm in a sand abrasion test, of not more than 59 mg.
- The resin composition according to the present invention is described in detail hereinafter. The resin composition of the present invention is a polyethylene resin composition (A) comprising a component (a-1) and a component (a-2) or a polyethylene resin composition (C) comprising the polyethylene resin composition (A) and further a polyolefin resin composition (B). First, the polyethylene resin composition (A) for use in the invention, which comprises the component (a-1) and the component (a-2), is described.
- The polyethylene resin composition (A) for use in the present invention comprises ultra-high-molecular weight polyethylene and low-molecular weight to high-molecular weight polyethylene, and is mainly used as a resin modifier.
- In the present invention, the ultra-high-molecular weight polyethylene and the low-molecular weight to high-molecular weight polyethylene for constituting the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) are each a homopolymer of ethylene or a copolymer of ethylene and an α-olefin, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene or 3-methyl-1-pentene.
- Of these, preferably used as the ultra-high-molecular weight polyethylene or the low-molecular weight to high-molecular weight polyethylene is a homopolymer of ethylene or a copolymer of ethylene and the above α-olefin which contains ethylene as a main ingredient.
- The ultra-high-molecular weight polyethylene (component (a-1)) for constituting the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) is polyethylene having an intrinsic viscosity [η], as measured in a decalin solvent at 135° C., of 10 to 40 dl/g, preferably 15 to 35 dl/g, more preferably 20 to 35 dl/g, and can be obtained by polymerization of the first step.
- On the other hand, the low-molecular weight to high-molecular weight polyethylene (component (a-2)) is polyethylene having an intrinsic viscosity [η], as measured in a decalin solvent at 135° C. similarly to the above, of 0.1 to 5 dl/g, preferably 0.5 to 3 dl/g, more preferably 1.0 to 2.5 dl/g, and can be obtained by polymerization of the second step after the formation of the ultra-high-molecular weight polyethylene. The polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) can be prepared by polymerizing ethylene in multiple steps in the presence of a catalyst, and the multi-step polymerization can be carried out in the same manner as the polymerization described in Japanese Patent Laid-Open Publication No. 289636/1990.
- By the use of the ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of the above range, a molded product having excellent abrasion resistance, self-lubricating properties, impact strength and chemical resistance can be obtained.
- In addition to the ultra-high-molecular weight polyethylene (component (a-1)), the low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of the above range is formed by the post-polymerization, whereby the compatibility with the later-described polyolefin resin composition (B) is enhanced, and as a result, the ultra-high-molecular weight polyethylene is homogeneously dispersed and combined. Hence, a polyethylene resin composition having an excellent balance of properties, such as abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance and moldability, particularly an excellent balance between abrasion resistance, appearance and moldability, can be obtained.
- In the present invention, the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) contains the ultra-high-molecular weight polyethylene (component (a-1)) and the low-molecular weight to high-molecular weight polyethylene (component (a-2)) in a specific ratio.
- That is to say, the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) contains the ultra-high-molecular weight polyethylene (component (a-1)) in an amount of more than 35% by weight and not more than 90% by weight, preferably more than 40% by weight and not more than 80% by weight, more preferably 45 to 80% by weight, and contains the low-molecular weight to high-molecular weight polyethylene (component (a-2)) in an amount of not less than 10% by weight and less than 65% by weight, preferably not less than 20% by weight and less than 60% by weight, more preferably 20 to 55% by weight. By setting the ratio between the ultra-high-molecular weight polyethylene (component (a-1)) and the low-molecular weight to high-molecular weight polyethylene (component (a-2)) in the above range, a resin composition containing ultra-high-molecular weight polyethylene of large particles can be obtained, and besides a resin composition can be improved in the compatibility with the polyolefin resin composition (B) and particularly excellent abrasion resistance, appearance and moldability can be obtained.
- The polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) substantially consists of the ultra-high-molecular weight polyethylene (component (a-1)) and the low-molecular weight to high-molecular weight polyethylene (component (a-2)).
- Accordingly, the sum of the content of the ultra-high-molecular weight polyethylene (component (a-1)) and the content of the low-molecular weight to high-molecular weight polyethylene (component (a-2)) in the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) is usually 100% by weight. The polyethylene resin composition (A), however, may contain, in addition to the above components, additives which may be added to ordinary polyolefins (such as stabilizer, e.g., heat stabilizer, weathering stabilizer, crosslinking agent, crosslinking assistant, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, filler, mineral oil type softener, petroleum resin and wax) within limits not detrimental to the objects of the present invention.
- The polyethylene resin composition (A) comprising the component (a-1) and the component (a-2), which substantially consists of the ultra-high-molecular weight polyethylene and the low-molecular weight to high-molecular weight polyethylene, has a density, as measured in accordance with ASTM D1505, of 930 to 980 kg/m3, preferably 940 to 980 kg/m3.
- The polyethylene resin composition (A) comprising the component (a-1) and the component (a-2.) has an intrinsic viscosity [η], as measured in a decalin solvent at 135° C., of 5 to 35 dl/g, preferably 10 to 30 dl/g, more preferably 12 to 28 dl/g.
- Since the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) has a density of the above range, a molded product of the composition has a low coefficient of dynamic friction and thereby exhibits excellent self-lubricating properties.
- Since the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) has an intrinsic viscosity [η] of the above range, the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B) can be well dispersed in each other.
- That is to say, the low-molecular weight to high-molecular weight polyethylene contained in the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B) are finely dispersed in each other to give a homogeneously dispersed state when they are melt blended by an extruder or the like. Therefore, by the use of the resin composition, a molded product having excellent abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance and moldability can be obtained.
- The polyethylene resin composition (A) can improve abrasion resistance, self-lubricating properties and the like when it is blended with other resins, so that it can be favorably used as a resin modifier. Although the resin to be modified is not specifically restricted, preferable is a polyolefin resin composition (B).
- The polyolefin resin composition (B) for use in the present invention is not specifically restricted as far as it is a resin composition containing at least an ethylene (co)polymer having an intrinsic viscosity [η] of 0.1 to 10 dl/g. Examples of the ethylene (co)polymers include high-pressure polyethylene, medium- or low-pressure polyethylene, an ethylene/α-olefin copolymer, an ethylene/vinyl alcohol copolymer, an ethylene/vinyl acetate copolymer, an ethylene/vinyl acetate copolymer saponified product, an ethylene/(meth)acrylic acid copolymer and an ethylene/α-olefin/diene (triene, polyene) terpolymer. Examples of the α-olefins include olefins of 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene and 3-methyl-1-pentene. Examples of the dienes (trienes, polyenes) include conjugated or non-conjugated dienes, trienes and polyenes, such as 5-ethylidene-2-norbornene and vinyl norbornene.
- The above ethylene (co)polymers may be used singly, or a resin composition composed of two or more of the ethylene (co)polymers may be used, or a resin composition composed of the ethylene (co)polymer and another polyolefin such as polypropylene or polybutene may be used.
- When the polyolefin resin composition (B) is polyethylene, the polyethylene has a density of 820 to 980 kg/m3, preferably 850 to 970 kg/m3, more preferably 860 to 960 kg/m3, and has an intrinsic viscosity [η] of 0.1 to 10 dl/g, preferably 0.2 to 8 dl/g, more preferably 0.3 to 6 dl/g.
- As the resin preferably contained in the polyolefin resin composition (B), not only the above-mentioned polyethylene having a density of 820 to 980 kg/m3 and an intrinsic viscosity [η] of 0.1 to 10 dl/g but also a resin composition composed of polypropylene and an ethylene/α-olefin/diene copolymer, or an ethylene/vinyl alcohol copolymer can be mentioned.
- Since the polyolefin resin composition (B) for use in the present invention is a resin composition containing at least the ethylene (co)polymer having an intrinsic viscosity [η] of 0.1 to 10 dl/g, the polyolefin resin composition (B) and the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) can be well dispersed in each other. That is to say, the polyolefin resin composition (B) and the low-molecular weight to high-molecular weight polyethylene contained in the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) are finely dispersed in each other to give a homogeneously dispersed state when they are melt blended by an extruder or the like. Therefore, by the use of the resin composition, a molded product having excellent abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance and moldability can be obtained.
- The polyolefin resin composition (B) in the present invention may contain additives which may be added to ordinary polyolefins (such as stabilizer, e.g., heat stabilizer, weathering stabilizer, crosslinking agent, crosslinking assistant, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, filler, mineral oil type softener, petroleum resin and wax) within limits not detrimental to the objects of the present invention.
- The polyethylene resin composition (C) according to the present invention comprises the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B).
- In the polyethylene resin composition (C) comprising the polyethylene resin composition (A) and the polyolefin resin composition (B), the compounding ratio between the polyethylene resin composition (A) and the polyolefin resin composition (B) is as follows: the proportion of the polyethylene resin composition (A) is in the range of 15 to 90% by weight and the proportion of the polyolefin resin composition (B) is in the range of 85 to 10% by weight; preferably, the proportion of the polyethylene resin composition (A) is in the range of 20 to 80% by weight and the proportion of the polyolefin resin composition (B) is in the range of 80 to 20% by weight; more preferably, the proportion of the polyethylene resin composition (A) is in the range of 40 to 60% by weight and the proportion of the polyolefin resin composition (B) is in the range of 60 to 40% by weight.
- The amount of the ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g contained in the polyethylene resin composition (C) is in the range of 2 to 40% by weight, preferably 5 to 30% by weight, more preferably 10 to 25% by weight.
- Since the polyethylene resin composition (C) of the present invention has the above-mentioned compounding ratios, the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B) can be well dispersed in each other.
- That. is to say, the polyolefin resin composition (B) and the low-molecular weight to high-molecular weight polyethylene contained in the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) are finely dispersed in each other to give a homogeneously dispersed state when they are melt blended by an extruder or the like.
- By the use of the resin composition (C), a molded product having excellent abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance, flexibility and moldability can be obtained.
- The polyethylene resin composition (C) of the present invention has a melt flow rate (MFR, 190° C., load of 10 kg) of not less than 6, preferably not less than 7, more preferably not less than 8. The sand abrasion wear of a sheet of 3 mm thickness obtained from the polyethylene resin composition (C), as measured in a sand abrasion test, is not more than 59 mg, preferably not more than 55 mg, more preferably not more than 52 mg. The limiting PV value of a sheet of 3 mm thickness obtained from the polyethylene resin composition (C) is not less than 0.30 (MPa·m/s), preferably not less than 0.35, more preferably not less than 0.40.
- The sum of the content of the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the content of the polyolefin resin composition (B) in the polyethylene resin composition (C) of the invention is 100% by weight. However, to the composition (C) of the invention may be added other resins within limits not detrimental to the objects of the present invention.
- The polyethylene resin composition (C) of the present invention contains, as its essential components, the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B), but to the composition (C) may be further added additives, such as filler, stabilizer, e.g., heat stabilizer, weathering stabilizer, crosslinking agent, crosslinking assistant, antistatic agent, slip agent, anti-blocking agent, anti-fogging agent, lubricant, dye, pigment, mineral oil type softener, petroleum resin and wax, within limits not detrimental to the objects of the present invention.
- Examples of ultraviolet absorbing agents as the weathering stabilizers arbitrarily added include benzophenone compounds, benzotriazole compounds, nickel compounds and hindered amine compounds. Specific examples of such compounds include 2,2′,4,4′-tetrahydroxybenzophenone, 2-(2′-hydroxy-3′-t-butyl-5′-butylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′-t-butyl-5′-butylphenyl)benzotriazole, nickel salt of bis(3,5-di-t-butyl-4-hydroxybenzoyl)phosphoric acid ethyl ester and bis(2,2′,6,6′-tetramethyl-4-piperidine)sebacate.
- Examples of the stabilizers arbitrarily added include phenolic antioxidants, such as tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester and 2,2′-oxamidobis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; and fatty acid metallic salts, such as zinc stearate, calcium stearate and calcium 1,2-hydroxystearate.
- The above compounds may be used in combination. For example, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane and zinc stearate or calcium stearate may be used in combination.
- Also employable as the stabilizers are, for example, phosphorus type stabilizers, such as distearyl pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl-4,4′-isopropylidenediphenol-pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, phenylbisphenol A-pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylene diphosphite and bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite.
- The above stabilizers can be used singly or in combination of two or more kinds.
- The polyethylene resin composition (C) of the present invention may contain organic fillers or inorganic fillers when needed, within limits not detrimental to the objects of the present invention.
- For example, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, glass flake, glass bead, Shirasu bead, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder and molybdenum sulfide may be contained.
- For preparing the polyethylene resin composition (C) of the present invention, a known process is applicable. For example, a melt blending process comprising preparing the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B) separately and melt kneading the polyethylene resin composition (A) and the polyolefin resin composition (B) by an extruder is available.
- In this process, kneading is carried out at a temperature at which both of the polyethylene resin composition (A) comprising the component (a-1) and the component (a-2) and the polyolefin resin composition (B) are melted, and the temperature is not specifically restricted. In general, melt kneading is carried out at a temperature of 180 to 400° C. As the extruder, an extruder used for ordinary polyolefin resins is employable, but from the viewpoint of kneading effect, a twin-screw extruder or a tandem extruder is preferable.
- In the present invention, a molded product of desired shape can be obtained by molding the polyethylene resin composition (C) by a known molding method.
- For example, by the use of various molding methods, such as injection molding, contour extrusion molding, pipe molding, tube molding, covering for molded product, injection blow molding, direct blow molding, T-die sheet or film molding, inflation molding and press molding, the polyethylene resin composition can be molded into products of various shapes, such as container, tray, sheet, bar and film, or into coverings of various molded products.
- Especially when the polyethylene resin composition (C) of the present invention is used to cover resin molded products, it is preferable to use co-extrusion molding.
- The molded products obtained as above can be widely applied to the conventionally known polyethylene uses. Because of their particularly excellent balance of properties, such as abrasion resistance, self-lubricating properties, impact strength and thin wall molding properties, the molded products can be applied to uses where such properties are required, for example, covering (lamination) of metallic products, such as steel pipe, electric wire and automobile slide door rail; covering (lamination) of various rubber products, such as pressure-resistant rubber hose, automobile door gasket, clean room door gasket, automobile glass run channel and automobile weather strip; lining of hopper and chute; and sliding materials, such as gear, bearing, roller, tape reel, various guide rails, elevator rail guide and various protective liners.
- When the polyethylene resin composition (C) is used as a covering material, the thickness of the covering material is in the range of 10 to 200 μm, preferably 20 to 100 μm. In the use of the polyethylene resin composition (C) as the covering (lamination) material, further, it is preferable that any sea-island structure is not observed on the surface of the resin composition by an electron microscope of 500× magnification, or even if it is observed, the island has an average particle diameter of not more than 20 μm.
- In the use of the polyethylene resin composition (C) as the covering (lamination) material, furthermore, the flexural modulus of the polyethylene resin composition (C) is desired to be not more than 1500 MPa, preferably not more than 1300 MPa, more preferably not more than 1000 MPa. In the use of the polyethylene resin composition (C) as the covering (lamination) material, moreover, the tensile elongation at break of the polyethylene resin composition (C) is desired to be not less than 10%, preferably not less than 20%, more preferably not less than 30%.
- The present invention is further described with reference to the following examples.
- The following examples have a character to aid in the understanding of the present invention and do not give grounds for the limitative interpretation of the present invention.
- Ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 30 dl/g and low-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 1.5 dl/g were produced in the weight ratio shown in Table 1 through two-step polymerization and then diluted by blending with, as the polyolefin resin composition (B), high-density low-molecular weight polyethylene (available from Mitsui Chemicals, Inc., trade name: Hizex 1700JP) having an intrinsic viscosity [η] of 1.1 dl/g and a density of 965 kg/m3 in the weight ratio shown in Table 1 so that the concentration of the ultra-high-molecular weight polyethylene (component (a-1)) in the resulting resin composition became 20% by weight. After the blending, the resin composition was melt blended by a PCM twin-screw extruder manufactured by Ikegai Ltd. to prepare pellets.
- The resultant blend (pellets) was subjected to injection molding to prepare a test piece (sheet having a thickness of 3 mm), and the test piece was subjected to evaluations, such as a sand abrasion test, a limiting PV value measuring test and visual observation of molded product appearance (dispersed state), in accordance with the test methods described later. The results are set forth in Table 1.
TABLE 1 Comp. Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 1 Ex. 2 Ex. 3 Ex. 3 Ex. 4 PE resin 20/80 35/65 41/59 50/50 75/25 95/5 100/0 composition (A) Ultra-high- molecular weight PE/PE (weight ratio) PE resin 100/0 57.1/42.9 49/51 40/60 26.7/73.3 21.1/78.9 20/80 Composition (A)/PO resin composition (B) (weight ratio) Proportion of 20 20 20 20 20 20 20 ultra-high- molecular weight PE after melt blending (wt %) Sand abrasion 64 62 51 50 47 60 65 wear (mg) Limiting PV 0.49 0.49 0.49 0.49 0.49 0.49 0.49 value (MPa · m/s) MFR (g/10 min) 6 10 8 7 14 16 32 Abrasion BB BB AA AA AA BB BB resistance Self- AA AA AA AA AA AA AA lubricating properties Injection AA AA AA AA AA AA AA moldability Molded product AA AA AA AA AA BB BB appearance (dispersed state) - Ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 30 dl/g and low-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 1.5 dl/g were produced in the weight ratio shown in Table 2 through two-step polymerization and then diluted by blending with, as the polyolefin resin composition (B), high-molecular weight polyethylene (available from Mitsui Chemicals, Inc., trade name: Hizex 5100E) having an intrinsic viscosity [η] of 2.6 dl/g and a density of 944 kg/m3 in the weight ratio shown in Table 2 so that the concentration of the ultra-high-molecular weight polyethylene (component (a-1)) in the resulting resin composition became 20% by weight. After the blending, the resin composition was melt blended by a PCM twin-screw extruder manufactured by Ikegai Ltd. to prepare pellets.
- The resultant blend (pellets) was subjected to injection molding to prepare a test piece (sheet having a thickness of 3 mm), and the test piece was subjected to a sand abrasion test and a limiting PV value measuring test in accordance with the test methods described later. Further, measurements of a flexural modulus and a tensile elongation at break of the test piece were carried out.
- By the use of an inflation film molding machine, molding of the blend into a tube having a thickness of 100 to 200 μm was attempted, and the moldability into tube and the tube appearance (dispersed state of ultra-high-molecular weight polyethylene) were evaluated. The results are set forth in Table 2.
TABLE 2 Comp. Comp. Comp. Comp. Ex. 5 Ex. 6 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 PE resin 20/80 35/65 41/59 50/50 75/25 95/5 100/0 composition (A) Ultra-high- molecular weight PE/PE (weight ratio) PE resin 100/0 57.1/42.9 49/51 40/60 26.7/73.3 21.1/78.9 20/80 composition (A)/PO resin composition (B) (weight ratio) Proportion of 20 20 20 20 20 20 20 ultra-high- molecular weight PE after melt blending (wt %) Sand abrasion 64 62 40 38 36 50 60 wear (mg) Limiting PV 0.49 0.39 0.35 0.32 0.30 0.20 0.19 value (MPa · m/s) Moldability Infea- Fea- Fea- Fea- Fea- Fea- Infea- into tube sible sible sible sible sible sible sible Abrasion BB BB AA AA AA AA BB resistance Self- AA AA AA AA AA BB BB lubricating properties Moldability BB AA AA AA AA BB BB Molded — AA AA AA AA BB — product appearance (dispersed state) Flexural 1630 1300 1200 1000 800 750 500 modulus (MPa) Tensile 8 50 180 250 100 5 3 elongation at break (%) - Linear polyethylene produced by two-step polymerization and containing ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 30 dl/g and low-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 1.5 dl/g in the weight ratio shown in Table 1 was diluted by blending with, as the polyolefin resin composition (B), high-density low-molecular weight polyethylene (available from Mitsui Chemicals, Inc., trade name: Hizex 1700JP) having an intrinsic viscosity [η] of 1.1 dl/g and a density of 965 kg/m3 in the weight ratio shown in Table 3. After the blending, the resin composition was melt blended by a PCM twin-screw extruder manufactured by Ikegai Ltd. to prepare pellets.
- The resultant blend (pellets) was subjected to injection molding to prepare a test piece (sheet having a thickness of 3 mm), and the test piece was subjected to evaluations, such as a sand abrasion test, a limiting PV value measuring test and visual observation of molded product appearance (dispersed state), in accordance with the test methods described later. The results are set forth in Table 3.
TABLE 3 Ref. Ref. Ref. Ref. Ex. 1 Ex. 7 Ex. 8 Ex. 2 Ex. 3 Ex. 9 Ex. 10 Ex. 4 PE resin 45/55 45/55 45/55 45/55 80/20 80/20 80/20 80/20 composition (A) Ultra-high- molecular weight PE/ PE (weight ratio) PE resin 8/92 20/80 85/15 95/5 8/92 20/80 85/15 92/8 composition (A)/PO resin composition (B) (weight ratio) Proportion of 3.6 9 38.3 42.8 6.4 12 68 73.6 ultra-high- molecular weight PE after melt blending (wt%) Sand 68 55 42 33 65 53 27 18 abrasion wear (mg) Limiting PV 0.49 0.49 0.49 0.49 0.49 0.49 0.49 0.49 value (MPa · m/s) MFR (g/- 20 15 7 1.7 18 10 6 0.8 10 min) Abrasion BB AA AA AA BB AA AA AA resistance Self- AA AA AA AA AA AA AA AA lubricating properties Injection AA AA AA BB AA AA AA BB moldability Molded BB AA AA BB BB AA AA PB product appearance (dispersed state) - Test methods
- Sand abrasion test
- In a stirring vessel, a mixture liquid of 3 kg of water and 2.6 kg of abrasive grains (JIS R6001 (A-43)) was placed, and 4 plates (test pieces) having a width of 25 mm, a length of 75 mm and a thickness of 3 mm were set on the stirring blade in such a manner that the angle between the plate and the mixture liquid was 45° . Then, the stirring blade was rotated at a rate of 1600 rpm for 3 hours to measure a sand abrasion wear. In a jacket of the stirring vessel, cooling water of 25° C. was circulated.
- The abrasion resistance was evaluated as follows. From the weight of the test piece before the test, the weight of the test piece after the test was subtracted to obtain an abrasion wear (mg) of the sample. A test piece having a sand abrasion wear of not more than 59 mg was evaluated as AA (pass). (Sand abrasion wear of conventional one (Comparative Example 1): not less than 60 mg) (See Table 1, Table 2 and Table 3)
- Limiting PV Value
- The self-lubricating properties were evaluated as follows. By the use of a metal plate (SUS-304) as a counter material, the test piece was abraded by a friction-abrasion tester (manufactured by KK Orientech, EFM-H1-ENS) with maintaining the peripheral velocity (V) constant at 0.2 m/s and increasing a load (P) every 30 minutes by 5 kg·f, and a load at which the test piece began to melt by frictional heat was measured to find a limiting PV value (MPa·m/s). A test piece having a limiting PV value of not less than 0.3 was evaluated as AA (pass). (Limiting PV value of ultra-high-molecular weight polyethylene conventionally used: not less than 0.28) (See Table 1, Table 2 and Table 3)
- MFR (Melt Flow Rate)
- As a measure of flowability, MFR was measured. A test piece having MFR of not lower than the MFR value (6 g/10 min) of a conventional one (Comparative Example 1) was evaluated as AA (pass) (see Table 1).
- Measuring temperature: 190° C.
- Load: 10 kg
- Flexural Modulus
- The flexural modulus was measured in accordance with ASTM D790.
- Tensile Elongation at Break
- The tensile elongation at break was measured in accordance with ASTM D638.
- Since the polyethylene resin composition according to the present invention comprises a polyethylene resin composition (A) comprising an ultra-high-molecular weight polyethylene component and a low-molecular weight to high-molecular weight polyethylene component or comprises the polyethylene resin composition (A) and a specific polyolefin resin composition (B), it has not only excellent abrasion resistance and mechanical properties inherent in the ultra-high-molecular weight polyethylene but also specific properties of the low-molecular weight to high-molecular weight polyethylene and/or the polyolefin resin composition (B). Hence, a molded product having an excellent balance of properties, such as abrasion resistance, self-lubricating properties, impact strength, chemical resistance, appearance, flexibility and molding properties, particularly an excellent balance between abrasion resistance, appearance and molding properties, can be obtained.
- Because of its excellent abrasion resistance, self-lubricating properties, appearance, flexibility and moldability, the polyethylene resin composition of the present invention can be favorably used as a material of an injection molded product, a covering (lamination) material for various molded products such as steel pipe, pressure-resistant rubber hose, electric wire and sheet, or a sliding material.
- An effect of the present invention is that a polyethylene resin composition exhibiting at least the following properties (1) to (4) at the same time can be provided.
- Another effect of the present invention is that a polyethylene resin composition, in a preferred embodiment, exhibiting the following properties (1) to (8) at the same time can be provided:
- (1) excellent mechanical properties (mechanical properties equal to or higher than those of conventional ultra-high-molecular weight polyethylene),
- (2) excellent abrasion resistance (abrasion resistance remarkably improved or enhanced as compared with that of conventional ultra-high-molecular weight polyethylene),
- (3) excellent appearance,
- (4) excellent moldability,
- (5) excellent self-lubricating properties,
- (6) excellent chemical resistance,
- (7) excellent impact resistance (impact strength), and
- (8) moderate flexibility.
Claims (9)
1. A resin modifier comprising a polyethylene resin composition (A) which comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 0.1 to 5 dl/g, wherein:
the amount of the component (a-1) is more than 35% by weight and not more than 90% by weight and the amount of the component (a-2) is not less than 10% by weight and less than 65% by weight, based on the total amount of the component (a-1) and the component (a-2), and
the polyethylene resin composition (A) has a density of 930 to 980 kg/m3 and an intrinsic viscosity [η] of 5 to 35 dl/g.
2. A polyethylene resin composition (C) comprising 15 to 90% by weight of a polyethylene resin composition (A) and 85 to 10% by weight of a polyolefin resin composition (B), wherein:
the polyethylene resin composition (A) comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 0.1 to 5 dl/g,
the amount of the component (a-1) is more than 35% by weight and not more than 90% by weight and the amount of the component (a-2) is not less than 10% by weight and less than 65% by weight, based on the total amount of the component (a-1) and the component (a-2),
the polyethylene resin composition (A) has a density of 930 to 980 kg/m3 and an intrinsic viscosity [η] of 5 to 35 dl/g, and
the polyolefin resin composition (B) contains at least an ethylene (co)polymer having an intrinsic viscosity [η] of 0.1 to 10 dl/g.
3. The polyethylene resin composition (C) as claimed in claim 2 , wherein the polyolefin resin composition (B) is polyethylene having a density of 820 to 980 kg/m3 and an intrinsic viscosity [η] of 0.1 to 10 dl/g.
4. The polyethylene resin composition (C) as claimed in claim 2 , wherein the polyolefin resin composition (B) is a resin composition containing polypropylene and an ethylene/α-olefin/diene copolymer.
5. The polyethylene resin composition (C) as claimed in claim 2 , wherein the polyolefin resin composition (B) contains an ethylene/vinyl alcohol copolymer.
6. A process for preparing a polyethylene resin composition which comprises ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g and low-molecular weight to high-molecular weight polyethylene (component (a-2)) having an intrinsic viscosity [η] of 0.1 to 5 dl/g, the amount of said component (a-1) being more than 35% by weight and not more than 90% by weight, the amount of said component (a-2) being not less than 10% by weight and less than 65% by weight, each amount being based on the total amount of the component (a-1) and the component (a-2), and which has a density of 930 to 980 kg/m3 and an intrinsic viscosity [η] of 5 to 35 dl/g,
comprising multi-step polymerization consisting of at least two steps of:
a first step of polymerizing ethylene in the presence of a Ziegler catalyst to form ultra-high-molecular weight polyethylene having an intrinsic viscosity [η] of 10 to 40 dl/g, and
a second step of polymerizing ethylene in the presence of the ultra-high-molecular weight polyethylene formed in the first step, a Ziegler catalyst and hydrogen to form low-molecular weight to high-molecular weight polyethylene having an intrinsic viscosity [η] of 0.1 to 5 dl/g.
7. The process for preparing a polyethylene resin composition as claimed in claim 6 , wherein the Ziegler catalyst comprises a high-activity titanium catalyst component containing magnesium, titanium and halogen as essential ingredients and an organoaluminum compound catalyst component.
8. A covering material or a sliding material made of a resin having a melt flow rate (190° C., load of 10 kg) of not less than 6, a sand abrasion wear, as measured on a sheet having a thickness of 3 mm in a sand abrasion test, of not more than 59 mg, and a limiting PV value, as measured on a sheet having a thickness of 3 mm, of not less than 0.30 (MPa·m/s).
9. A covering material or a sliding material comprising a resin composition containing at least 2 to 40% by weight of ultra-high-molecular weight polyethylene (component (a-1)) having an intrinsic viscosity [η] of 10 to 40 dl/g, and
having a sand abrasion wear, as measured on a sheet having a thickness of 3 mm in a sand abrasion test, of not more than 59 mg.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001-270550 | 2001-09-06 | ||
JP2001270550 | 2001-09-06 | ||
PCT/JP2002/008982 WO2003022920A1 (en) | 2001-09-06 | 2002-09-04 | Polyethylene resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040039115A1 true US20040039115A1 (en) | 2004-02-26 |
Family
ID=19096190
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/415,365 Abandoned US20040039115A1 (en) | 2001-09-06 | 2002-09-04 | Polyethylene resin composition |
Country Status (6)
Country | Link |
---|---|
US (1) | US20040039115A1 (en) |
JP (1) | JP4173444B2 (en) |
KR (1) | KR20040015015A (en) |
CN (1) | CN1473174A (en) |
BR (1) | BR0205962A (en) |
WO (1) | WO2003022920A1 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070010626A1 (en) * | 2005-07-11 | 2007-01-11 | Shankernarayanan Manivakkam J | Polyethylene compositions |
EP1973444A1 (en) * | 2006-01-13 | 2008-10-01 | 3M Innovative Properties Company | Integrally molded brush and the method of manufacture and its uses thereof |
US20110207840A1 (en) * | 2008-11-19 | 2011-08-25 | Mitsui Chemicals, Inc. | Polyolefin resin composition and uses thereof |
US20120095168A1 (en) * | 2010-10-18 | 2012-04-19 | Kornfield Julia A | Methods and systems for synthesis of an ultra high molecular weight polymer |
US20130087362A1 (en) * | 2010-03-17 | 2013-04-11 | Borealis Ag | Polymer composition for w&c application with advantageous electrical properties |
WO2014091501A1 (en) * | 2012-12-13 | 2014-06-19 | Reliance Industries Limited | Easily processable ultrahigh molecular weight polyethylene and a process for preparation thereof |
US9096746B2 (en) | 2011-08-31 | 2015-08-04 | Mitsui Chemicals, Inc. | Polyolefin resin composition and applications thereof |
WO2017077455A3 (en) * | 2015-11-02 | 2017-07-20 | Reliance Industries Limited | A process for preparation of high melt strength polyolefin composition |
US20190055384A1 (en) * | 2016-02-29 | 2019-02-21 | Setsunankasei Co., Ltd. | Resin composition and molded article using resin composition |
US10336843B2 (en) | 2016-03-25 | 2019-07-02 | Asahi Kasei Kabushiki Kaisha | Ultra-high molecular weight ethylene-based copolymer powder, and molded article using ultra-high molecular weight ethylene-based copolymer powder |
KR20190124829A (en) * | 2010-03-17 | 2019-11-05 | 보레알리스 아게 | Polymer composition for w&c application with advantageous electrical properties |
CN113388192A (en) * | 2021-04-20 | 2021-09-14 | 长泰铱科科技有限公司 | High-toughness low-temperature-resistant highlight regenerated PP (polypropylene) modified material and preparation method thereof |
US11952480B2 (en) | 2018-02-05 | 2024-04-09 | Exxonmobil Chemical Patents Inc. | Enhanced processability of LLDPE by addition of ultra-high molecular weight density polyethylene |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005314544A (en) * | 2004-04-28 | 2005-11-10 | Asahi Kasei Chemicals Corp | Ultra-high-molecular-weight polyethylene resin composition and molded article made thereof |
JP2006052287A (en) * | 2004-08-11 | 2006-02-23 | Sunallomer Ltd | Flame-retardant polyolefin-based resin composition |
JP2007023171A (en) * | 2005-07-19 | 2007-02-01 | Mitsui Chemicals Inc | Ultra-high-molecular-weight polyethylene particulate excellent in heat resistance and method for producing the same |
EP2341085B1 (en) * | 2006-07-25 | 2012-10-03 | Mitsui Chemicals, Inc. | Ethylene polymer particles, production method thereof and molded article using the same |
US8137551B1 (en) | 2008-08-08 | 2012-03-20 | Kx Technologies, Llc | Push filter with floating key lock |
US9901852B2 (en) | 2008-08-08 | 2018-02-27 | Kx Technologies Llc | Push filter with floating key lock |
EP2371896B1 (en) * | 2008-12-26 | 2014-02-12 | Mitsui Chemicals, Inc. | Ethylene polymer composition, manufacturing method therefor, and molded article obtained using same |
JP5672531B2 (en) * | 2010-10-13 | 2015-02-18 | 東ソー株式会社 | Biodegradable resin composition for foaming and foamed molded article |
JP6570172B2 (en) * | 2014-08-29 | 2019-09-04 | 三菱ケミカルアドバンスドマテリアルズ株式会社 | Conductive resin composition and resin molded body |
KR101629251B1 (en) * | 2014-10-21 | 2016-06-10 | 삼익티에이치케이 주식회사 | Composition for resin products containing oil and lubrication products using this |
JP7306796B2 (en) * | 2017-06-05 | 2023-07-11 | 旭化成株式会社 | Polyethylene-based resin composition, polyethylene-based film |
JP6487591B1 (en) | 2017-09-07 | 2019-03-20 | 旭化成株式会社 | Ultra high molecular weight ethylene polymer powder and molded product using ultra high molecular weight ethylene polymer powder |
KR102626057B1 (en) | 2019-02-20 | 2024-01-18 | 아사히 가세이 가부시키가이샤 | polyethylene powder |
JP2021152140A (en) | 2020-03-24 | 2021-09-30 | 旭化成株式会社 | Polyethylene powder, and molding |
CN111745927B (en) * | 2020-06-30 | 2022-01-28 | 中国石油化工科技开发有限公司 | High-wear-resistance high-lubrication polyethylene product and preparation method thereof |
CN113121902B (en) * | 2021-03-23 | 2022-11-22 | 江西铜业股份有限公司 | Rapid forming ultra-high molecular weight polyethylene pipe and preparation method thereof |
CN114163763B (en) * | 2021-12-27 | 2023-12-22 | 复旦大学 | Polyethylene compound capable of thermoplastic processing |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4933393A (en) * | 1987-11-13 | 1990-06-12 | Mitsui Petrochemical Industries, Ltd. | Polyolefin composition |
US5019627A (en) * | 1986-07-04 | 1991-05-28 | Mitsui Petrochemical Industries, Ltd. | Injection-molding polyolefin composition |
US5079287A (en) * | 1987-11-05 | 1992-01-07 | Mitsui Petrochemical Industries, Ltd. | Olefin resin composition for injection molding |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63175069A (en) * | 1987-01-14 | 1988-07-19 | Mitsui Petrochem Ind Ltd | Additive for improving low frictional properties of synthetic resin |
JP3372059B2 (en) * | 1992-07-29 | 2003-01-27 | 新日本石油化学株式会社 | Ethylene / α-olefin copolymer composition |
JP3372057B2 (en) * | 1992-07-29 | 2003-01-27 | 新日本石油化学株式会社 | Ethylene polymer composition |
JP3375169B2 (en) * | 1993-02-26 | 2003-02-10 | 新日本石油化学株式会社 | Polyethylene resin composition |
JP3375167B2 (en) * | 1993-02-26 | 2003-02-10 | 新日本石油化学株式会社 | Ethylene polymer composition |
JP3375168B2 (en) * | 1993-02-26 | 2003-02-10 | 新日本石油化学株式会社 | Polyethylene composition |
DE4309456A1 (en) * | 1993-03-24 | 1994-09-29 | Hoechst Ag | Polyethylene compositions for injection molding |
JPH0812771A (en) * | 1994-06-28 | 1996-01-16 | Dainippon Printing Co Ltd | Ultrahigh-molecular-weight polyethylene molding and its production |
-
2002
- 2002-09-04 KR KR10-2003-7005611A patent/KR20040015015A/en not_active Application Discontinuation
- 2002-09-04 WO PCT/JP2002/008982 patent/WO2003022920A1/en not_active Application Discontinuation
- 2002-09-04 BR BR0205962-2A patent/BR0205962A/en not_active Application Discontinuation
- 2002-09-04 US US10/415,365 patent/US20040039115A1/en not_active Abandoned
- 2002-09-04 JP JP2003526989A patent/JP4173444B2/en not_active Expired - Lifetime
- 2002-09-04 CN CNA028028422A patent/CN1473174A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5019627A (en) * | 1986-07-04 | 1991-05-28 | Mitsui Petrochemical Industries, Ltd. | Injection-molding polyolefin composition |
US5079287A (en) * | 1987-11-05 | 1992-01-07 | Mitsui Petrochemical Industries, Ltd. | Olefin resin composition for injection molding |
US4933393A (en) * | 1987-11-13 | 1990-06-12 | Mitsui Petrochemical Industries, Ltd. | Polyolefin composition |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070010626A1 (en) * | 2005-07-11 | 2007-01-11 | Shankernarayanan Manivakkam J | Polyethylene compositions |
EP1973444A4 (en) * | 2006-01-13 | 2013-04-10 | 3M Innovative Properties Co | Integrally molded brush and the method of manufacture and its uses thereof |
EP1973444A1 (en) * | 2006-01-13 | 2008-10-01 | 3M Innovative Properties Company | Integrally molded brush and the method of manufacture and its uses thereof |
US20110207840A1 (en) * | 2008-11-19 | 2011-08-25 | Mitsui Chemicals, Inc. | Polyolefin resin composition and uses thereof |
US8349957B2 (en) | 2008-11-19 | 2013-01-08 | Mitsui Chemicals, Inc. | Polyolefin resin composition and uses thereof |
KR101959473B1 (en) * | 2010-03-17 | 2019-03-18 | 보레알리스 아게 | Polymer composition for w&c application with advantageous electrical properties |
KR20190124829A (en) * | 2010-03-17 | 2019-11-05 | 보레알리스 아게 | Polymer composition for w&c application with advantageous electrical properties |
KR20130051928A (en) * | 2010-03-17 | 2013-05-21 | 보레알리스 아게 | Polymer composition for w&c application with advantageous electrical properties |
US10811164B2 (en) | 2010-03-17 | 2020-10-20 | Borealis Ag | Polymer composition for W and C application with advantageous electrical properties |
US10626265B2 (en) | 2010-03-17 | 2020-04-21 | Borealis Ag | Polymer composition for W and C application with advantageous electrical properties |
KR102094653B1 (en) * | 2010-03-17 | 2020-03-30 | 보레알리스 아게 | Polymer composition for w&c application with advantageous electrical properties |
US20130087362A1 (en) * | 2010-03-17 | 2013-04-11 | Borealis Ag | Polymer composition for w&c application with advantageous electrical properties |
US10208196B2 (en) * | 2010-03-17 | 2019-02-19 | Borealis Ag | Polymer composition for W and C application with advantageous electrical properties |
US20120095168A1 (en) * | 2010-10-18 | 2012-04-19 | Kornfield Julia A | Methods and systems for synthesis of an ultra high molecular weight polymer |
US10150860B2 (en) * | 2010-10-18 | 2018-12-11 | California Institute Of Technology | Methods and systems for synthesis of an ultra high molecular weight polymer |
US20160040002A1 (en) * | 2010-10-18 | 2016-02-11 | California Institute Of Technology | Methods and systems for synthesis of an ultra high molecular weight polymer |
US9127096B2 (en) * | 2010-10-18 | 2015-09-08 | California Institute Of Technology | Methods and systems for synthesis of an ultra high molecular weight polymer |
US9096746B2 (en) | 2011-08-31 | 2015-08-04 | Mitsui Chemicals, Inc. | Polyolefin resin composition and applications thereof |
KR101988698B1 (en) | 2012-12-13 | 2019-06-12 | 릴라이언스 인더스트리즈 리미티드 | Easily processable ultrahigh molecular weight polyethylene and a process for preparation thereof |
US9624363B2 (en) | 2012-12-13 | 2017-04-18 | Reliance Industries Limited | Easily processable ultrahigh molecular weight polyethylene and a process for preparation thereof |
KR20150094650A (en) * | 2012-12-13 | 2015-08-19 | 릴라이언스 인더스트리즈 리미티드 | Easily processable ultrahigh molecular weight polyethylene and a process for preparation thereof |
WO2014091501A1 (en) * | 2012-12-13 | 2014-06-19 | Reliance Industries Limited | Easily processable ultrahigh molecular weight polyethylene and a process for preparation thereof |
WO2017077455A3 (en) * | 2015-11-02 | 2017-07-20 | Reliance Industries Limited | A process for preparation of high melt strength polyolefin composition |
US20190055384A1 (en) * | 2016-02-29 | 2019-02-21 | Setsunankasei Co., Ltd. | Resin composition and molded article using resin composition |
US10336843B2 (en) | 2016-03-25 | 2019-07-02 | Asahi Kasei Kabushiki Kaisha | Ultra-high molecular weight ethylene-based copolymer powder, and molded article using ultra-high molecular weight ethylene-based copolymer powder |
US11952480B2 (en) | 2018-02-05 | 2024-04-09 | Exxonmobil Chemical Patents Inc. | Enhanced processability of LLDPE by addition of ultra-high molecular weight density polyethylene |
CN113388192A (en) * | 2021-04-20 | 2021-09-14 | 长泰铱科科技有限公司 | High-toughness low-temperature-resistant highlight regenerated PP (polypropylene) modified material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
WO2003022920A1 (en) | 2003-03-20 |
BR0205962A (en) | 2003-10-07 |
CN1473174A (en) | 2004-02-04 |
JPWO2003022920A1 (en) | 2004-12-24 |
JP4173444B2 (en) | 2008-10-29 |
KR20040015015A (en) | 2004-02-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20040039115A1 (en) | Polyethylene resin composition | |
JP5340292B2 (en) | Filled TPO composition with good low temperature ductility | |
WO2011131579A1 (en) | Automotive interior compound | |
JP2007514043A (en) | Thermoplastic olefin-based composition | |
KR100620475B1 (en) | Olefinic Thermoplastic Elastomer, Process for Production Thereof, Olefinic Thermoplastic Elastomer Compositions, Process for Producing the Same and Moldings thereof | |
JP3270322B2 (en) | Thermoplastic resin composition with improved mold contamination | |
US6204328B1 (en) | Polyolefin resin composition | |
US5288806A (en) | Thermoplastic olefins with low viscosity | |
JPH09208761A (en) | Polyolefin-based resin composition | |
JP2008208303A (en) | Propylenic resin composition, its production method and injection molded article | |
JP3255266B2 (en) | gasket | |
JP5661439B2 (en) | Method for producing thermoplastic polymer | |
JP2006083251A (en) | Polypropylene resin composition and injection molded product made of the same | |
JP2019044110A (en) | Dynamic crosslinking type thermoplastic elastomer composition for non-foam molding | |
WO2019117185A1 (en) | Propylene-based resin composition and article molded from same | |
JP7119869B2 (en) | THERMOPLASTIC ELASTOMER COMPOSITION AND JOINTING MEMBER | |
WO2020171019A1 (en) | Olefin polymer composition and molded body of same | |
KR101835343B1 (en) | Master batch composition, resin composition including the same and molded article produced therefrom | |
JPH03197542A (en) | Resin composition for blow molding | |
JP2019044112A (en) | Dynamic crosslinking type thermoplastic elastomer composition for composite molding and composite molded body | |
JPH08231789A (en) | Thermoplastic elastomer composition | |
JP2001114838A (en) | Ethylene-alpha-olefin copolymer | |
WO2024058210A1 (en) | Sliding composition and use thereof, and method for producing sliding composition | |
WO2023276571A1 (en) | Thermoplastic elastomer composition and molded body of same | |
JP2022087985A (en) | Resin composition and molding |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: MITSUI CHEMICALS, INC., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ISHIDA, YUKIO;REEL/FRAME:014529/0666 Effective date: 20030324 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |